X-ray Diffraction

(XRD)

Oleh:
Victor Kayadoe, S.Pd., M.Si

Program Studi Pendidikan Kimia

FKIP Universitas Pattimura
Leofanti, 1997
 X-Ray Diffraction
Principle: interference of photons by reflection by ordered structures

Interference positive for:

 2 
n = 2d sin  Bragg’s law


So, identification compound

d sin  d

In real catalysts: line broadening

the smaller the crystals the more line broadening

So, from XRD crystallite diameter D = K / (b cos )

D can be estimated
b = peak width
K = constant; usually ca. 1
 Schematic of X-Ray
Diffractometer
Ionisation chamber
rotates 2 degrees when
the crystal rotates 
Crystal


2 XRD patterns: fingerprints of

X-ray source
ordered solids
XRD: unambiguous
information on crystal
Detector
structure
Active Phase of Industrial Catalysts is
Microcrystalline
a. b.
2 = 180o

Photographic film 111

200
200
Diffraction line
220
Undeviated X-rays 220
222 311
400 222
420 400

422 331
420
422
440
511
600 333
442
620 440
Sample 531
622
600
444 442
640 620
533
642 622

444
Incident X-rays 711
551
640

2 = 0o

X-Ray Diffraction Data: KCl NaCl

 Uses: different structures 53 816-ICSD
Lamb da: 1 .54 178 Magnif: 1. 0 F WHM: 0.2 00
Space g rp: F m -3 m Direct cell: 5 .6 400 5. 640 0 5. 64 00 90. 00 9 0. 00 90. 00

Even if two structures are the

same (and they are chemically NaCl
similar) differences can be
observed:
Peak positions (unit cell changes)
and relative intensities (atoms)
2053 825-ICSD 30 40 50 60 70
Lamb da: 1 .54 178 Magnif: 1. 0 F WHM: 0.2 00
Space g rp: F m -3 m Direct cell: 6 .2 800 6. 280 0 6. 28 00 90. 00 9 0. 00 90. 00

KCl

There is another major point

here:
K+ and Cl- are isoelectronic 20 30 40 50 60 70
 Uses: polymorphs

Different
polymorphs will
have different
powder patterns
e.g. Zn S
Uses: polymorphs
K3SO4F: tetragonal &
cubic forms
 M

M = Monoclinic
M T = Tetragonal

M
T
M

SZ700

Int
en
sit
y/
SZ600
a.
u.

SZ500

1/3 X
SZ100
XRD pattern of the
Zr(SO4)2 calcined at the
20 25 30 35 40 various temperature for 6
2, degree
h.
 Peak Broadening
In an X-ray diffraction pattern, peak width
depends on
• the instrument
– radiation not pure monochromatic
– Heisenberg uncertainty principle
– focussing geometry

• the sample…
- a crystalline substance gives rise to sharp
lines, whereas a truly amorphous material
gives a broad “hump”.
 Peak Broadening
If crystal size < 0.2 m, then peak broadening occurs
At <50nm, becomes significant.
Why?
Bragg’s law gives the condition for constructive
interference.
At slightly higher  than the Bragg angle, each plane gives
a “lag” in the diffracted beam.
For many planes, these end up cancelling out and thus the
net diffraction is zero.

In small crystals, there are relatively fewer planes, so there

is a “remanent” diffraction
 Peak Broadening
We can calculate the average size of the crystals from the
broadening:
0.9
t Scherrer formula
B cos B
t is the thickness of the crystal,  the wavelength, B the
Bragg angle.
B is the line broadening, by reference to a standard, so
that
B  BM  BS
2 2 2

where BS is the halfwidth of the standard material in

radians. (A normal halfwidth is around 0.1o)
 Uses: particle size determination
Here we see particle size increasing with temperature
200

150
1050oC
100

50
30oC
0
15 20 25 30 35 40 45 50 55 60
20 / o
 Amorphous / micro-crystalline?
It can be difficult to distinguish between an amorphous
material and a crystalline sample with very small particle
size.
BUT the idea of such a small size “crystal” being
crystalline doesn’t make sense!
5nm = 50Å = e.g. 10 unit cells
Is this sufficient for long range order??
 Uses: more advanced
Structure refinement – the Rietveld method

A refinement technique, not determination Hugo Rietveld,

b1932

Whole-pattern fitting - not just the Bragg reflections

Needs a MODEL - pattern calculated from model, compared

point-by-point with observed pattern.

Originally developed (1967,1969) for use with neutron data

- good reproducible peak shapes
1977 - first report of application to X-ray data
http://home.wxs.nl/~rietv025/
 Uses: Rietveld Refinement
x y z
Here there was a similarity Ca/Ce 0.3333 0.6667 -0.0038(18)
between the powder pattern of Ce 0.2337(4) -0.0108 0.25
this phase and an existing one Si 0.403(3) 0.380(3) 0.25

– also chemical composition O1 0.316(4) 0.467(4) 0.25

O2 0.597(5) 0.467(4) 0.25
similar. O3 0.340(2) 0.252(3) 0.071(3)
O4 0 0 0.25

J. M. S. Skakle, C. L. Dickson, F. P. Glasser, Powder Diffraction (2000) 15, 234-238

 Uses: more advanced
• Quantitative phase analysis (how much of each)
Naïve approach - relative intensity of peak maxima?
- Consider mixture of Ba,Si,O
- Ba component would scatter more than Si component
(e.g. Ba2SiO4 c.f. SiO2)
1,600 HA 80.18 %
1,400 b-TCP 19.82 %
Thus uses Rietveld 1,200
1,000
method and takes
Counts

800
into account relative 600
400
scattering from each 200
crystalline phase 0
-200
-400
10 20 30 40 50 60
2Th Degrees
 Summary
Many different uses for powder X-ray diffraction!
 Fingerprinting: identifying phases, distinguishing
similar materials, identifying polymorphs, (following
chemical reactions)
 Indication of particle size from peak broadening
 Unit cell refinement
 Variable temperature/pressure measurements
 Crystal structure refinement
 Quantitative analysis
 Kinetic study
 X-Ray Diffraction Patterns
WO3/SiO2-W

wt% WO3
100

37
WO3/SiO2 20
WO3
12
6 (1.5 -100 wt%)
3

1.5

60 50 40 30 20 10
2 (degrees)

WO3/Al2O3-D

wt% WO3
29
13
WO3
WO3/Al2O3 7.4
3.6
1.8
0.9
(0 -29 wt%)
0

70 60 50 40 30 20 10
2 (degrees)
 Solid-State Diffusion of Co into Al2O3
9.1 wt% CoO/Al2O3
* bulk CoAl2O4
o
Calcination T: 1290 K
n

1025 k

h
875 g

675 d

a
380
80 70 60 50 40 30 20
2 (degrees)
2-line position of “Al2O3 and CoAl2O4”
diffraction line at about 80 degrees
Above 900 K the intensity of spinel lines increases,
Al2O3 lines shift:

79.6

79.4
2 (degrees)

79.2

79.0

78.8

600 800 1000 1200

Calcination temperature (K)

Conclusion: above 800 K Co2+ diffuses into the bulk

Change of Unit Cell Size vs Calcination
Temperature

791.0
NiO(4.1)/Al2O3
792.7
a
794.4 NiO(5.1)WO3/Al2O3

796.0
calculated
797.7

675 875 1075

Calcination temperature (K)
Crystallinity